EP0084853B1 - Process for the preparation of 1,8-naphtholactam compounds - Google Patents

Process for the preparation of 1,8-naphtholactam compounds Download PDF

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EP0084853B1
EP0084853B1 EP83100441A EP83100441A EP0084853B1 EP 0084853 B1 EP0084853 B1 EP 0084853B1 EP 83100441 A EP83100441 A EP 83100441A EP 83100441 A EP83100441 A EP 83100441A EP 0084853 B1 EP0084853 B1 EP 0084853B1
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formula
alkyl
compound
naphtholactone
bisulfite
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EP0084853A1 (en
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Rainer Dr. Begrich
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/90—Benzo [c, d] indoles; Hydrogenated benzo [c, d] indoles
    • C07D209/92—Naphthostyrils

Definitions

  • the invention relates to a process for the preparation of 1,8-naphtholactam compounds of the formula wherein R is hydrogen, an optionally C 1 -C 4 alkoxy, halogen, hydroxy, cyano, carboxy, N, N-dialkyl (C 1 -C 4) carbamoyl or phenyl substituted C 1 -C 4 alkyl radical, a cyclohexyl radical or an optionally by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, cyano, carboxy, N, N-dialkyl (C 1 -C 4 ) carbamoyl or N, N-dialkyl (C 1 -C 4 ) -sulfamoyl is substituted phenyl and the benzene rings A and / or B are optionally substituted by halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4
  • the C 1 -C 4 -alkyl radical in which it is a radical R or a substituent on the phenyl radical or the benzene rings A and / or B, can be unbranched or branched. It is, for example, the methyl, ethyl, n-propyl or tert-butyl radical.
  • the alkyl radical R can be substituted, for. B. by a C l -C 4 alkoxy group, such as the methoxy, ethoxy, n-propoxy, n-butoxy or sec-butoxy group.
  • Halogen atoms such as, for. B. fluorine, chlorine or bromine in question.
  • the phenyl radical R can not only by C 1 -C 4 alkyl, but z. B. can also be substituted by halogen, such as fluorine, chlorine or bromine or a branched or unbranched alkoxy radical having 1 to 4 carbon atoms.
  • the rings of the naphthalene skeleton A and B can also be substituted by a C 1 to C 4 alkyl radical.
  • substituents are mentioned halogen, such as fluorine, chlorine or bromine, furthermore C 1 -C 4 alkoxy, namely an unbranched or branched alkoxy radical, such as. B. methoxy; Aethoxy or n-propoxy radical.
  • the C 1 -C 4 alkylsulfonyl radical is, for. B. the methylsulfonyl or ethylsulfonyl group and in the alkyl (C 1 -C 4 ) carbonylamino group in the first place. around the acetylamino residue.
  • the N, N-dibutylsulfamoyl group (dibutylaminosulfonyl group) is mentioned, for example, as the N, N-dialkyl (C 1 -C 4 ) sulfamoyl group.
  • the new process is carried out by reacting a 1,8-naphtholactone compound of the formula II, preferably in an aqueous medium, with an amine of the formula 111, if appropriate in the presence of a bisulfite.
  • a lower aliphatic alcohol such as. B. methanol can be used.
  • the reaction is advantageously carried out in the presence of a bisulfite.
  • a bisulfite As bisulfite z. B. alkali, ammonium and alkaline earth bisulfites in question such as especially sodium bisulfite or calcium bisulfite.
  • the bisulfite is preferably added in the form of an aqueous solution (e.g. 40% aqueous solution).
  • the reaction according to the present invention proceeds particularly well (based on the yield of the naphtholactam compound of the formula I) when working with 2 to 10 equivalents and in particular 2 to 5 equivalents of the amine of the formula III and in the presence of bisulfite. It is advantageous to use 0.1 to 5 equivalents and in particular 0.5 to 2.5 equivalents of bisulfite, based on the 1,8-naphtholactone of the formula 11 used.
  • the reaction is preferably carried out in an autoclave for about 1 to 24 hours at a temperature of about 100 to 200 ° C. At a temperature of 150 ° C, the reaction is e.g. B. ended after about 15 hours. The reaction mass is then allowed to cool and filtered or the liquid phases are separated.
  • the 1,8-naphtholactam compounds of the formula I are obtained in high purity and with a yield of over 90%, based on the lactone compound used.
  • the amines of the formula III are likewise known or can be prepared by known methods; the following can be used, for example, in the process according to the invention: ammonia, methylamine, ethylamine, n-propylamine, methoxyethylamine, 2-cyanoethylamine, 3-hydroxypropylamine, chloromethylamine, methanolamine; Aniline, anisidine (o-, m-, p-), chloraniline, toluidine, xylidine, aminobenzonitrile, aminobenzoic acid, dimethylanthranilamide and diethylsulfanilamide.
  • 1,8-naphtholactam compounds of the formula obtained by the process according to the invention can be used as intermediates in dye synthesis, e.g. B. for the production of acid and disperse dyes, but also of cationic dyes by known processes (see, for example, EP-A-0 017 621).
  • the process according to the present invention is distinguished above all from the known processes for the preparation of the naphtholactam compounds of the formula I by its economy.
  • lactones which are derived from hydroxy acids with an aliphatic hydroxyl group to the corresponding lactams or N-alkyllactams, depending on whether the reaction is carried out with ammonia or an amine, has already been described in the literature. So z. B. in Theilheimer Vol. 29; 201 (1975) the synthesis of an intermediate of the alkaloid dendrobin. A 1,7-hexahydroindanone lactone is then reacted with methylamine to give the corresponding N-methyllactam. The reaction is carried out in hydrochloric acid.
  • isocoumarin which is also derived from a hydroxycarboxylic acid with an aliphatic, here ⁇ , ⁇ -unsaturated, hydroxyl group, with ammonia to give isocarbostyril is described in Houben-Weyl, Vol. VI / 2, page 793 (1963).
  • lactones derived from hydroxy acids with a phenolic hydroxyl group do not form lactams with ammonia or amines [Houben-Weyl Vol XI / 2, page 539 (1958)].
  • the unsubstituted 1,8-naphtholactam can also be obtained by carrying out the reaction as indicated in Example 1, but without adding bisulfite.
  • the product obtained in this way is identical by thin layer chromatography to the 1,8-naphtholactam obtained according to Example 1.
  • 1,8-naphtholactam can also be prepared as follows: 8.5 parts of 1,8-naphtholactone and 19.0 parts of sodium bisulfite are mixed in 40 parts of methanol and then 25 parts of a saturated solution of ammonia in methanol are added. After 15 hours at 150 ° C. and 14 bar in an autoclave, 1,8-naphtholactam is obtained in good yield, which is identical to the product prepared in Example 1 according to the thin layer chromatogram and the melting point.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von 1,8-Naphtholactamverbindungen der Formel

Figure imgb0001
worin R Wasserstoff, ein gegebenenfalls durch C1-C4-Alkoxy, Halogen, Hydroxy, Cyano, Carboxy, N,N-Dialkyl(C1-C4)-carbamoyl oder Phenyl substituierter C1-C4-Alkylrest, ein Cyclohexylrest oder ein gegebenenfalls durch Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, Cyano, Carboxy, N,N-Dialkyl(C1-C4)-carbamoyl- oder N,N-Dialkyl(C1-C4)-sulfamoyl substituierter Phenylrest ist und die Benzolringe A und/oder B gegebenenfalls durch Halogen, Cyano, Nitro, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkylsulfonyl, Phenylsulfonyl, Alkyl-(C1-C4)-carbonylamino, Benzoylamino, Carboxyl, C1-C4-Alkoxycarbonyl, Carbamoyl, N-Mono- oder N,N-Dialkyl-(C1-C4)-carbamoyl, Sulfamoyl, N-Mono- oder N,N-Dialkyl-(C1-C4)-sulfamoyl substituiert sind. Das neue Verfahren ist dadurch gekennzeichnet, dass man eine 1,8-Naphtholactonverbindung der Formel II
Figure imgb0002
mit einem Amin der Formel 111
Figure imgb0003
gegebenenfalls in Gegenwart von Bisulfit umsetzt.The invention relates to a process for the preparation of 1,8-naphtholactam compounds of the formula
Figure imgb0001
 wherein R is hydrogen, an optionally C 1 -C 4 alkoxy, halogen, hydroxy, cyano, carboxy, N, N-dialkyl (C 1 -C 4) carbamoyl or phenyl substituted C 1 -C 4 alkyl radical, a cyclohexyl radical or an optionally by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, cyano, carboxy, N, N-dialkyl (C 1 -C 4 ) carbamoyl or N, N-dialkyl (C 1 -C 4 ) -sulfamoyl is substituted phenyl and the benzene rings A and / or B are optionally substituted by halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylsulfonyl, phenylsulfonyl carbamoyl, alkyl (C 1 -C 4) carbonylamino, benzoylamino, carboxyl, C 1 -C 4 alkoxycarbonyl, carbamoyl, N-mono- or N, N-dialkyl (C 1 -C 4) sulfamoyl, N-mono- or N, N-dialkyl- (C 1 -C 4 ) sulfamoyl are substituted. The new process is characterized in that a 1,8-naphtholactone compound of the formula II
Figure imgb0002
 with an amine of formula 111
Figure imgb0003
 if appropriate in the presence of bisulfite.

Der C1-C4-Alkylrest, bei es als Rest R oder als Substituent des Phenylrestes oder der Benzolringe A und/oder B, kann unverzweigt oder verzweigt sein. Es handelt sich beispielsweise um den Methyl-, Aethyl-, n-Propyl- oder tert.-Butylrest. Der Alkylrest R kann substituiert sein und zwar z. B. durch eine Cl-C4-Alkoxygruppe, wie die Methoxy-, Aethoxy-, n-Propoxy-, n-Butoxy- oder sec.-Butoxygruppe. Als Substituenten kommen ferner Halogenatome, wie z. B. Fluor, Chlor oder Brom in Frage. Der Phenylrest R kann nicht nur durch C1-C4-Alkyl, sondern z. B. auch durch Halogen, wie Fluor, Chlor oder Brom oder einen verzweigten bzw. unverzweigten Alkoxyrest mit 1 bis 4 C-Atomen substituiert sein.The C 1 -C 4 -alkyl radical, in which it is a radical R or a substituent on the phenyl radical or the benzene rings A and / or B, can be unbranched or branched. It is, for example, the methyl, ethyl, n-propyl or tert-butyl radical. The alkyl radical R can be substituted, for. B. by a C l -C 4 alkoxy group, such as the methoxy, ethoxy, n-propoxy, n-butoxy or sec-butoxy group. Halogen atoms such as, for. B. fluorine, chlorine or bromine in question. The phenyl radical R can not only by C 1 -C 4 alkyl, but z. B. can also be substituted by halogen, such as fluorine, chlorine or bromine or a branched or unbranched alkoxy radical having 1 to 4 carbon atoms.

Die Ringe des Naphthalingerüstes A und B können, wie bereits erwähnt, ebenfalls durch einen C1 bis C4-Alkylrest substituiert sein. Als weitere Substituenten sind genannt Halogen, wie Fluor, Chlor oder Brom, ferner C1-C4-Alkoxy und zwar ein unverzweigter oder verzweigter Alkoxyrest, wie z. B. der Methoxy; Aethoxy- oder n-Propoxyrest. Bei dem C1-C4-Alkylsulfonylrest handelt es sich z. B. um die Methylsulfonyl- oder Aethylsulfonylgruppe und bei der Alkyl (C1-C4)-carbonylaminogruppe in erster Linie . um den Acetylaminorest. Als N,N-Dialkyl-(C1-C4)-sulfamoylgruppe ist beispielsweise die N,N-Dibutylsulfa- moylgruppe (Dibutylaminosulfonylgruppe) genannt.As already mentioned, the rings of the naphthalene skeleton A and B can also be substituted by a C 1 to C 4 alkyl radical. As further substituents are mentioned halogen, such as fluorine, chlorine or bromine, furthermore C 1 -C 4 alkoxy, namely an unbranched or branched alkoxy radical, such as. B. methoxy; Aethoxy or n-propoxy radical. The C 1 -C 4 alkylsulfonyl radical is, for. B. the methylsulfonyl or ethylsulfonyl group and in the alkyl (C 1 -C 4 ) carbonylamino group in the first place. around the acetylamino residue. The N, N-dibutylsulfamoyl group (dibutylaminosulfonyl group) is mentioned, for example, as the N, N-dialkyl (C 1 -C 4 ) sulfamoyl group.

Das neue Verfahren wird derart durchgeführt, dass man eine 1,8-Naphtholactonverbindung der Formel II vorzugsweise im wässrigen Medium mit einem Amin der Formel 111, gegebenenfalls in Gegenwart eines Bisulfits umsetzt. Dabei kann man entweder die Verbindung der Formel II in Wasser suspendieren und das Amin oder die wässrige Lösung des Amins der Formel 111 zugeben, oder man legt das Amin der Formel 111 oder seine wässrige Lösung vor und gibt die Verbindung der Formel II eventuell als wässrige Suspension zu ; es ist aber auch möglich, dass man die Verbindung der Formel II mit dem Amin der Formel III mischt und anschliessend gegebenenfalls Wasser zufügt. Anstelle des Wassers kann als Reaktionsmedium auch ein niederer aliphatischer Alkohol, wie z. B. Methanol, verwendet werden.The new process is carried out by reacting a 1,8-naphtholactone compound of the formula II, preferably in an aqueous medium, with an amine of the formula 111, if appropriate in the presence of a bisulfite. You can either suspend the compound of formula II in water and add the amine or the aqueous solution of the amine of formula 111, or you can submit the amine of formula 111 or its aqueous solution and possibly give the compound of formula II as an aqueous suspension to; however, it is also possible to mix the compound of the formula II with the amine of the formula III and then, if appropriate, to add water. Instead of water, a lower aliphatic alcohol, such as. B. methanol can be used.

Vorteilhaft wird die Reaktion in Gegenwart eines Bisulfits durchgeführt. Als Bisulfits kommen z. B. Alkali-, Ammonium- und Erdalkalibisulfite in Frage wie vor allem Natriumbisulfit oder auch Calciumbisulfit. Es ist aber auch möglich Gemische verschiedener Bisulfite der Reaktion zuzusetzen oder auch das Bisulfit-Salz des Amins der Formel III. Man setzt das Bisulfit vorzugsweise in Form einer wässrigen Lösung (z. B. 40 %ige wässrige Lösung) zu.The reaction is advantageously carried out in the presence of a bisulfite. As bisulfite z. B. alkali, ammonium and alkaline earth bisulfites in question such as especially sodium bisulfite or calcium bisulfite. However, it is also possible to add mixtures of different bisulfites to the reaction or to add the bisulfite salt of the amine of the formula III. The bisulfite is preferably added in the form of an aqueous solution (e.g. 40% aqueous solution).

Die Umsetzung gemäss vorliegender Erfindung verläuft besonders gut (bezogen auf die Ausbeute an der Naphtholactamverbindung der Formel I), wenn man mit 2 bis 10 Aequivalent und insbesondere 2 bis 5 Aequivalenten des Amins der Formel III und in Gegenwart von Bisulfit arbeitet. Vorteilhaft setzt man 0,1 bis 5 Aequivalente und insbesondere 0,5 bis 2,5 Aequivalente des Bisulfits, bezogen auf das eingesetzte 1,8-Naphtholacton der Formel 11, ein.The reaction according to the present invention proceeds particularly well (based on the yield of the naphtholactam compound of the formula I) when working with 2 to 10 equivalents and in particular 2 to 5 equivalents of the amine of the formula III and in the presence of bisulfite. It is advantageous to use 0.1 to 5 equivalents and in particular 0.5 to 2.5 equivalents of bisulfite, based on the 1,8-naphtholactone of the formula 11 used.

Die Durchführung der Reaktion erfolgt vorzugsweise in einem Autoklaven während ca. 1 bis 24 Stunden bei einer Temperatur von etwa 100 bis 200 °C. Bei einer Temperatur von 150 °C ist die Reaktion z. B. nach ca. 15 Stunden beendet. Anschliessend lässt man die Reaktionsmasse abkühlen und filtriert oder trennt die flüssigen Phasen. Man erhält dabei die 1,8-Naphtholactamverbindungen der Formel I in hoher Reinheit und mit einer Ausbeute von über 90 %, bezogen auf die eingesetzte Lactonverbindung.The reaction is preferably carried out in an autoclave for about 1 to 24 hours at a temperature of about 100 to 200 ° C. At a temperature of 150 ° C, the reaction is e.g. B. ended after about 15 hours. The reaction mass is then allowed to cool and filtered or the liquid phases are separated. The 1,8-naphtholactam compounds of the formula I are obtained in high purity and with a yield of over 90%, based on the lactone compound used.

Die Naphtholactonverbindungen der Formel II sind bekannt oder können nach bekannten Methoden hergestellt werden. Erfindungsgemäss werden beispielsweise die folgenden eingesetzt :

  • Naphtholacton-1,8 ;
  • 4-Chlor-naphtholacton-1,8 ;
  • 4-Brom-naphtholacton-1,8 ;
  • 2,4-Dibrom-naphtholacton-1,8 ;
  • 5-Cyan-naphtholacton-1,8 ;
  • 4-Methylsulfonyl-naphtholacton-1,8 ;
  • 4-Dibutylaminosulfonyl-naphtholacton-1,8 ;
  • 5-Aethyloxycarbonyl-naphtholacton-1,8 ; und
  • 5-N-Methyl-carbamoyl-naphtholacton-1,8
The naphtholactone compounds of the formula II are known or can be prepared by known methods. According to the invention, the following are used, for example:
  • Naphtholactone-1.8;
  • 4-chloro-naphtholactone-1,8;
  • 4-bromo-naphtholactone-1.8;
  • 2,4-dibromo-naphtholactone-1,8;
  • 5-cyano-naphtholactone-1,8;
  • 4-methylsulfonyl-naphtholactone-1,8;
  • 4-dibutylaminosulfonyl-naphtholactone-1,8;
  • 5-ethyloxycarbonyl-naphtholactone-1,8; and
  • 5-N-methyl-carbamoyl-naphtholactone-1,8

Bekannt oder nach bekannten Methoden herstellbar sind ebenfalls die Amine der Formel III ; die folgenden können beispielsweise im erfindungsgemässen Verfahren eingesetzt werden : Ammoniak, Methylamin, Aethylamin, n-Propylamin, Methoxyäthylamin, 2-Cyanäthylamin, 3-Hydroxypropylamin, Chlormethylamin, Methanolamin ; Anilin, Anisidin (o-, m-, p-), Chloranilin, Toluidin, Xylidin, Aminobenzonitril, Aminobenzoesäure, Dimethylanthranilamid und Diäthylsulfanilamid.The amines of the formula III are likewise known or can be prepared by known methods; the following can be used, for example, in the process according to the invention: ammonia, methylamine, ethylamine, n-propylamine, methoxyethylamine, 2-cyanoethylamine, 3-hydroxypropylamine, chloromethylamine, methanolamine; Aniline, anisidine (o-, m-, p-), chloraniline, toluidine, xylidine, aminobenzonitrile, aminobenzoic acid, dimethylanthranilamide and diethylsulfanilamide.

Die gemäss dem erfindungsgemässen Verfahren erhaltenen 1,8-Naphtholactamverbindungen der Formel können als Zwischenprodukte in der Farbstoffsynthese verwendet werden, z. B. zur Herstellung von Säure- und Dispersionsfarbstoffen, aber auch von kationischen Farbstoffen nach bekannten Verfahren (siehe z. B. EP-A-0 017 621).The 1,8-naphtholactam compounds of the formula obtained by the process according to the invention can be used as intermediates in dye synthesis, e.g. B. for the production of acid and disperse dyes, but also of cationic dyes by known processes (see, for example, EP-A-0 017 621).

Das Verfahren gemäss der vorliegenden Erfindung zeichnet sich gegenüber den bekannten Verfahren zur Herstellung der Naphtholactamverbindungen der Formel I vorallem durch seine Wirtschaftlichkeit aus.The process according to the present invention is distinguished above all from the known processes for the preparation of the naphtholactam compounds of the formula I by its economy.

Verbindungen der Formel I mit R = H werden nach bekannten Verfahren z. B. derart erhalten, dass man 1-Naphthylamin mit Phosgen umsetzt und dann den Lactamring nach Friedel-Crafts mit AlCl3 schliesst. Man gelangt auch zur gleichen Verbindung, wenn man 1,8-Naphthalindicarbonsäureanhydrid mit Hydroxylamin und anschliessend mit Tosylchlorid zum N-Tosyloxy-1,8-Naphthalindicarbimid umsetzt und dieses nach Lossen abbaut. Verbindungen der Formel I, worin R nicht H ist, erhält man mittels einer mehrstufigen Synthese über die Verbindung I mit R = H und z. B. nachfolgender Alkylierung ; es handelt sich also durchweg um mehrstufige Verfahren.Compounds of formula I with R = H are z. B. obtained in such a way that 1-naphthylamine is reacted with phosgene and then the lactam ring according to Friedel-Crafts is closed with AlCl 3 . The same compound is also obtained if 1,8-naphthalenedicarboxylic anhydride is reacted with hydroxylamine and then with tosyl chloride to give N-tosyloxy-1,8-naphthalenedicarbimide and the latter is broken down according to Lossen. Compounds of the formula I in which R is not H are obtained by means of a multi-stage synthesis via the compound I with R = H and z. B. Subsequent alkylation; all of them are multi-stage processes.

Die Umsetzung von Lactonen, die sich von Hydroxysäuren mit aliphatischer Hydroxygruppe ableiten zu den entsprechenden Lactamen oder N-Alkyllactamen, je nachdem, ob man die Reaktion mit Ammoniak oder einem Amin durchführt, ist bereits in der Literatur beschrieben. So z. B. im Theilheimer Bd. 29 ; 201 (1975) die Synthese einer Zwischenstufe des Alkaloids Dendrobin. Danach wird ein 1,7-Hexahydroindanonlacton mit Methylamin zum entsprechenden N-Methyllactam umgesetzt. Die Reaktion wird in Salzsäure durchgeführt. Die Umsetzung von Isocumarin, das sich ebenfalls von einer Hydroxycarbonsäure mit aliphatischer, hier α,β-ungesättigter Hydroxygruppe, ableitet, mit Ammoniak zum lsocarbostyril ist im Houben-Weyl Bd. VI/2, Seite 793 (1963), beschrieben. Daneben findet sich jedoch in der Literatur der Hinweis, dass Lactone, die sich von Hydroxysäuren mit phenolischer Hydroxylgruppe ableiten, mit Ammoniak oder Aminen keine Lactame bilden [Houben-Weyl Bd XI/2, Seite 539 (1958)].The conversion of lactones which are derived from hydroxy acids with an aliphatic hydroxyl group to the corresponding lactams or N-alkyllactams, depending on whether the reaction is carried out with ammonia or an amine, has already been described in the literature. So z. B. in Theilheimer Vol. 29; 201 (1975) the synthesis of an intermediate of the alkaloid dendrobin. A 1,7-hexahydroindanone lactone is then reacted with methylamine to give the corresponding N-methyllactam. The reaction is carried out in hydrochloric acid. The reaction of isocoumarin, which is also derived from a hydroxycarboxylic acid with an aliphatic, here α, β-unsaturated, hydroxyl group, with ammonia to give isocarbostyril is described in Houben-Weyl, Vol. VI / 2, page 793 (1963). In addition, however, there is a reference in the literature that lactones derived from hydroxy acids with a phenolic hydroxyl group do not form lactams with ammonia or amines [Houben-Weyl Vol XI / 2, page 539 (1958)].

Die nachfolgenden Beispiele veranschaulichen die Erfindung, ohne sie darauf zu limitieren. Teile bedeuten, sofern nichts anderes angegeben ist, Gewichtsteile und die Temperaturen sind in Grad Celsius angegeben.The following examples illustrate the invention without restricting it to them. Unless otherwise stated, parts mean parts by weight and the temperatures are given in degrees Celsius.

Beispiel 1example 1

In einem Autoklaven werden 20 ml (ca. 5 Aequivalente) wässriges Ammoniak vorgelegt und 8,5 g 1,8-Naphtholacton (in kristalliner Form) langsam eingetragen. Nach einigen Minuten Rühren werden 20 ml (ca. 2 Aequivalente) NaHSO3-Lösung (40 %ige wässrige Lösung) zugegeben. Anschliessend wird im Autoklaven für 15 Stunden bei 150 °C gerührt (Druck ca. 7,5 bar). Sodann wird mit ca. 100 ml Wasser verdünnt und abgesaugt. Der Rückstand wird mit ca. 200 ml Wasser gewaschen und im Vakuum getrocknet. Man erhält 7,7 g (= 91 % bezogen auf das eingesetzte 1,8-Naphtholacton) der Naphtholactamverbindung der Formel20 ml (approx. 5 equivalents) of aqueous ammonia are placed in an autoclave and 8.5 g of 1,8-naphtholactone (in crystalline form) are slowly introduced. After stirring for a few minutes, 20 ml (approx. 2 equivalents) of NaHSO 3 solution (40% strength aqueous solution) are added. The mixture is then stirred in an autoclave at 150 ° C. for 15 hours (pressure about 7.5 bar). Then it is diluted with about 100 ml of water and suction filtered. The residue is washed with about 200 ml of water and dried in vacuo. 7.7 g (= 91% based on the 1,8-naphtholactone used) of the naphtholactam compound of the formula are obtained

Figure imgb0004
welche einen Schmelzpunkt (roh) von 180° aufweist.
Figure imgb0004
 which has a melting point (raw) of 180 °.

Beispiel 2Example 2

Man löst 4,1 T 3-Methyl-N-methyl-benzomorpholin in 12,5 T Dichloräthan, gibt nacheinander 4,2 T 1,8-Naphtholactam, erhalten gemäss Beispiel 1, 3 T Phosphorpentoxyd und 10 T Phosphoroxytrichlorid zu und erwärmt auf 80°. Man kondensiert während 1 Stunde bei 81-83°, kühlt auf 25°, tropft langsam 100 T Wasser zu und stellt mit einer wässrigen Lösung von Natriumhydroxyd auf pH ca. 9. Man extrahiert mit 200 T Essigester und destilliert das Lösungsmittel ab. Man erhält so 7,5 T des Farbstoffes der Formel

Figure imgb0005
welcher z. B. mit Essigsäure protoniert in Wasser löslich wird. Man erhält mit dieser Lösung eine rotstichig blaue Färbung auf Polyacrylnitrilfasern mit sehr guten Allgemeinechtheiten.4.1 parts of 3-methyl-N-methylbenzomorpholine are dissolved in 12.5 parts of dichloroethane, 4.2 parts of 1,8-naphtholactam are added in succession, 3 parts of phosphorus pentoxide and 10 parts of phosphorus oxytrichloride are added according to Example 1 and the mixture is warmed up 80 °. It is condensed for 1 hour at 81-83 °, cooled to 25 °, slowly added dropwise 100 T water and adjusted to pH approx. 9 with an aqueous solution of sodium hydroxide. It is extracted with 200 T ethyl acetate and the solvent is distilled off. This gives 7.5 T of the dye of the formula
Figure imgb0005
 which z. B. protonated with acetic acid becomes soluble in water. This solution gives a reddish blue color on polyacrylonitrile fibers with very good general fastness properties.

Beispiel 3Example 3

Das unsubstituierte 1,8-Naphtholactam lässt sich auch erhalten, indem man die Reaktion wie in Beispiel 1 angegeben durchführt, jedoch kein Bisulfit zusetzt. Das so erhaltene Produkt ist dünnschichtchromatographisch identisch mit gemäss Beispiel 1 erhaltenem 1,8-Naphtholactam.The unsubstituted 1,8-naphtholactam can also be obtained by carrying out the reaction as indicated in Example 1, but without adding bisulfite. The product obtained in this way is identical by thin layer chromatography to the 1,8-naphtholactam obtained according to Example 1.

Beispiel 4Example 4

1,8-Naphtholactam lässt sich auch wie folgt herstellen : 8,5 Teile 1,8-Naphtholacton und 19,0 Teile Natriumbisulfit werden in 40 Teilen Methanol vermischt und danach 25 Teile einer gesättigten Lösung von Ammoniak in Methanol zugegeben. Nach 15 Stunden bei 150 °C und 14 bar im Autoklaven erhält man in guter Ausbeute 1,8-Naphtholactam, das mit dem im Beispiel 1 hergestellten Produkt nach dem Dünnschichtchromatogramm wie auch dem Schmelzpunkt, identisch ist.1,8-naphtholactam can also be prepared as follows: 8.5 parts of 1,8-naphtholactone and 19.0 parts of sodium bisulfite are mixed in 40 parts of methanol and then 25 parts of a saturated solution of ammonia in methanol are added. After 15 hours at 150 ° C. and 14 bar in an autoclave, 1,8-naphtholactam is obtained in good yield, which is identical to the product prepared in Example 1 according to the thin layer chromatogram and the melting point.

Beispiele 5 bis 22Examples 5 to 22

Arbeitet man wie in den Beispielen 1, 3 oder 4 beschrieben, setzt jeweils das Naphtholacton aus Spalte 1 der folgenden Tabelle mit dem Amin aus der Spalte 2 um, so erhält man in guter Ausbeute und hoher Qualität das in Spalte 3 aufgeführte Naphtholactam, dessen Schmelzpunkt in Spalte 4 angegeben ist.
(Siehe Schema Seite 5 ff.)

Figure imgb0006
Figure imgb0007
Figure imgb0008
 If one works as described in Examples 1, 3 or 4, the naphtholactone from column 1 of the following table is reacted with the amine from column 2, the naphtholactam listed in column 3 and its melting point are obtained in good yield and high quality is indicated in column 4.
(See diagram on page 5 ff.)
Figure imgb0006
Figure imgb0007
Figure imgb0008

Claims (5)

1. A process for the preparation of a 1,8-naphtholactam compound of the formula I
Figure imgb0012
wherein R is hydrogen, a C1-C4-alkyl group which is unsubstituted or substituted by C1-C4-alkoxy, halogen, hydroxy, cyano, carboxy, N,N-di-(C1-C4-alkyl)-carbamoyl or phenyl, or is a cyclohexyl group, or a phenyl group which in unsubstituted or substituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, cyano, carboxy, N,N-di-(C1-C4-alkyl)-carbamoyl or N,N-di-(C1-C4-alkyl)-sulfamoyl, and the benzene rings A and/or B are unsubstituted or substituted by halogen, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C4- alkylsulfonyl, phenylsulfonyl, C1-C4-alkylcarbonylamino, benzoylamino, carboxy, C1-C4-alkoxycarbonyl, carbamoyl, N-mono- or N,N-di-(C1-C4-alkyl)-carbamoyl, sulfamoyl, N-mono- or N,N-di-(C1-C4-alkyl)-sulfamoyl, which process comprises reacting a 1,8-naphtholactone compound of the formula II
Figure imgb0013
with an amine of the formula III
Figure imgb0014
in the absence or presence of bisulfite.
2. A process according to claim 1, wherein the reaction is performed in an aqueous medium.
3. A process according to either of claims 1 or 2, wherein the reaction of the compound II with the amine of the formula III is performed in the presence of bisulfite.
4. A process according to any one of claims 1 to 3, which comprises the use of 2 to 10 equivalents of the amine of the formula III and 0.1 to 5 equivalents of the bisulfite compound, based in each case on the 1,8-naphtholactone compound of the formula II.
5. A process according to claim 4, which comprises the use of 2 to 5 equivalents of the amine of the formula III and 0.5 to 2.5 equivalents of the bisulfite compound, based in each case on the 1,8-naphtholactone compound of the formula II.
EP83100441A 1982-01-22 1983-01-19 Process for the preparation of 1,8-naphtholactam compounds Expired EP0084853B1 (en)

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EP0017621A1 (en) * 1979-04-04 1980-10-15 Ciba-Geigy Ag Derivatives of naphtholactam, process for their preparation and their use as dyestuffs

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US3347865A (en) * 1967-10-17 Hybrocarbon-z-tertiary amino carbo- cvclic aryl benz-[c,d]-indoles
CH521976A (en) * 1969-12-23 1972-04-30 Sandoz Ag Benzindolyl-guanidine derivs - with sympathomimetic salidiuretic and antiphlogistic activity
US4246410A (en) * 1976-06-01 1981-01-20 Ciba -Geigy Aktiengesellschaft Naphtholactam dyestuffs
US4261896A (en) * 1979-11-23 1981-04-14 American Cyanamid Company 1-Substituted-2-(substituted-imino)-1H-1,2-dihydrobenz[cd]indoles

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Title
Houben-Weyl Band VI/2, Seite 793-4 *
Houben-Weyl Band XI/2, Seite 539 *
Synthetic Methods of Organic Chemistry Band 29 (1975), Seite 201 (387) *

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